Membrane biofouling is one of major issues impeding the applications of polyvinylidene fluoride (PVDF) membrane for water and wastewater treatment. In this work, quaternary ammonium compounds loaded on silica nanopollens (QAC@SNP) were developed to modify polyvinylidene fluoride (PVDF) membrane for mitigating biofouling. The modified membrane (M-Si-Q) by QAC@SNP demonstrated efficient antibacterial efficiency against E. coli (inhibition rate ~98.2%) and S. aureus (inhibition rate ~99.9%) compared to the control (M0), respectively. The inhibition rate of M-Si-Q was also higher than the membrane blended with silica nanopollens (M-Si) (~86.1% of E. coli and ~70.9% of S. aureus, respectively), suggesting the synergetic effects of SNP and QAC for biofouling mitigation. Batch filtration tests showed that M-Si-Q could effectively alleviate the decline of membrane permeate flux compared to the control. Confocal laser scanning microscope analysis of membrane samples after fouling showed that almost all of cells on the M-Si-Q membrane were dead cells, while abundant live cells were observed for the M-Si and M0. Moreover, the M-Si-Q membrane had less quantity of proteins on the surface, demonstrating that M-Si-Q had excellent antibiofouling ability. The above findings indicated a strong potential of using QAC@SNP to fabricate antibiofouling membranes for water and wastewater treatment.